Energy Barrier For Water Dissociation Research Articles

Grain Boundary Tailors the Local Chemical Environment on Iridium Surface for Alkaline Electrocatalytic Hydrogen Evolution

AbstractEven though grain boundaries (GBs) have been previously employed to increase the number of active catalytic sites or tune the binding energies of reaction intermediates for promoting electrocatalytic reactions, the effect of GBs on the tailoring of the local chemical environment on the catalyst surface has not been clarified thus far. In this study, a GBs‐enriched iridium (GB−Ir) was synthesized and examined for the alkaline hydrogen evolution reaction (HER). Operando Raman spectroscopy and density functional theory (DFT) calculations revealed that a local acid‐like environment with H3O+ intermediates was created in the GBs region owing to the electron‐enriched surface Ir atoms at the GBs. The H3O+ intermediates lowered the energy barrier for water dissociation and provided enough hydrogen proton to promote the generation of hydrogen spillover from the sites at the GBs to the sites away from the GBs, thus synergistically enhancing the hydrogen evolution activity. Notably, the GB−Ir catalyst exhibited a high alkaline HER activity (10 mV @ 10 mA cm−2, 20 mV dec−1). We believe that our findings will promote further research on GBs and the surface science of electrochemical reactions.

Grain Boundary Tailors the Local Chemical Environment on Iridium Surface for Alkaline Electrocatalytic Hydrogen Evolution.

Even though grain boundaries (GBs) have been previously employed to increase the number of active catalytic sites or tune the binding energies of reaction intermediates for promoting electrocatalytic reactions, the effect of GBs on the tailoring of the local chemical environment on the catalyst surface has not been clarified thus far. In this study, a GBs-enriched iridium (GB-Ir) was synthesized and examined for the alkaline hydrogen evolution reaction (HER). Operando Raman spectroscopy and density functional theory (DFT) calculations revealed that a local acid-like environment with H3 O+ intermediates was created in the GBs region owing to the electron-enriched surface Ir atoms at the GBs. The H3 O+ intermediates lowered the energy barrier for water dissociation and provided enough hydrogen proton to promote the generation of hydrogen spillover from the sites at the GBs to the sites away from the GBs, thus synergistically enhancing the hydrogen evolution activity. Notably, the GB-Ir catalyst exhibited a high alkaline HER activity (10 mV @ 10 mA cm-2 , 20 mV dec-1 ). We believe that our findings will promote further research on GBs and the surface science of electrochemical reactions.

Multi‐Interface Engineering of Self‐Supported Nickel/Yttrium Oxide Electrode Enables Kinetically Accelerated and Ultra‐Stable Alkaline Hydrogen Evolution at Industrial‐Level Current Density

AbstractThe development of highly active and robust non‐noble‐metal electrocatalysts for alkaline hydrogen evolution reaction (HER) at industrial‐level current density is the key for industrialization of alkaline water electrolysis. Herein, a superhydrophilic self‐supported Ni/Y2O3 heterostructural electrocatalyst is constructed by a high‐temperature selective reduction method, which demonstrates excellent catalytic performance for alkaline HER at high current density. Concretely, this catalyst can drive 10 mA cm−2 at a low overpotential of 61.1 ± 3.7 mV, with a low Tafel slope of 52.8 mV dec−1. Moreover, it also shows outstanding long‐term durability at high current density of 1000 mA cm−2 for 500 h in 1 m KOH, evidently exceeding the metallic Ni and Pt/C(20%) catalysts. The superior HER activity can be attributed to the multi‐interface engineering of the Ni/Y2O3 electrode. Construction of Ni/Y2O3 heterogeneous interface with dual active sites lowers the energy barrier of water dissociation and optimizes the hydrogen adsorption energy, thus synergistically accelerating the overall HER kinetics. Also, its superhydrophilic self‐supported electrode structure with the firm electrocatalyst‐substrate interface and weakened electrocatalyst‐bubble interfacial force ensures rapid charge transfer, prevents catalyst shedding, and expedites the H2 gas bubble release timely, further enhancing the catalytic activity and stability at high current density.

Boosting hydrogen evolution performance of nanoporous Fe-Pd alloy electrocatalyst by metastable phase engineering

Nanoporous Fe-Pd alloy with metastable face-centered cubic (fcc Fe-Pd) phase is prepared by electrochemical dealloying as an electrocatalyst for hydrogen evolution reaction (HER). The nanoporous fcc Fe-Pd alloy achieves an overpotential of 58 mV at 10 mA cm−2 in 1 M KOH, outperforming those of stable body-centered cubic Fe-Pd alloy (bcc Fe-Pd) and commercial Pt/C catalyst. Density functional theory calculation reveals that the metastable fcc structure can tailor the coordination environment and electronic structure of Pd active sites in Fe-Pd alloy. As a result, the d‐band center of Pd active site shifts away from the Fermi level, which weakens the Pd-H interaction and reduces the energy barrier of water dissociation. In addition, the fcc Fe-Pd exhibits good mechanical properties, which maintains the catalytic performance in the deformation state. This work broadens the idea for designing and preparing HER catalysts via metastable phase structure design.

Modulating the Electronic Interactions via Heterostructure Engineering for Energy-Saving Hydrogen Production at High Current Densities

The advanced alkaline hydrogen evolution reaction (HER) catalysts should have low water dissociation energy barrier and fast reaction kinetics. However, the single component transition metal catalysts usually show insufficient activation...

Revealing The Role of Electronic Asymmetricity on Supported Ru Nanoclusters for Alkaline Hydrogen Evolution Reaction

AbstractModulating the electronic asymmetricity of catalysts is an effective method for optimizating the elementary steps of water dissociation and hydrogen adsorption/desorption process for the alkaline hydrogen evolution reaction (HER). Herein, uniform Ru nanoclusters anchored on N doped ultrathin carbon nanosheets (Ru/NC) are synthesized to optimize the asymmetricity electronic properties of supported Ru for efficient HER. It is found that Ru and NC with a large work function difference (ΔΦ) leading to the formation of stronger asymmetrical charge distributions of Ru that electron‐deficient high‐valence Ru (Run+) coupling with low‐valence Ru (Ru0). Experimental and theoretical studies indicate the Run+ sites lowered the energy barrier for water dissociation and provided enough hydrogen proton to promote the hydrogen spillover from the Run+ to Ru0 sites, and Ru0 sites can enhance H desorption process, thus synergistically enhancing the hydrogen evolution activity. Notably, the Ru/NC catalyst exhibits a high alkaline HER activity (21.9 mV@10 mA cm−2, 29.03 mV dec−1). The role of electronic asymmetricity on supported Ru nanoclusters for the alkaline HER are demonstrated, which will provide guidelines for the rational design of high‐efficiency alkaline HER catalysts.

Tetra-Coordinated W2 S3 for Efficient Dual-pH Hydrogen Production.

Two-dimensional (2D) transition-metal dichalcogenides (TMDs) have emerged as promising catalysts for the hydrogen evolution reaction (HER) that play a crucial role in renewable energy technologies. Breaking the inherent structural paradigm limitations of 2D TMDs is the key to exploring their fascinating physical and chemical properties, which is expected to develop a revolutionary HER catalyst. Herein, we unambiguously present metallic W2 S3 instead of energetically favorable WS2 via a unique stoichiometric growth strategy. Benefiting from the excellent conductivity and hydrophilicity of the tetra-coordinated structure, as well as an appropriate Gibbs free energy value and an enough low energy barrier for water dissociation, the W2 S3 as catalyst achieves Pt-like HER activity and high long-term stability in both acidic and alkaline electrolytes. For application in proton exchange membrane (PEM) and anion exchange membrane (AEM) electrolysers, W2 S3 as the cathode catalyst yields excellent bifunctionality index (ɳ =1.73 V, ɳ =1.77 V) and long-term stability (471 h@PEM with a decay rate of 85.7 μV h-1 , 360 h@AEM with a decay rate of 27.1 μV h-1 ). Our work provides significant insight into the tetra-coordinated W2 S3 and facilitates the development of advanced electrocatalysts for sustainable hydrogen production.

Tetra‐Coordinated W2S3 for Efficient Dual‐pH Hydrogen Production

AbstractTwo‐dimensional (2D) transition‐metal dichalcogenides (TMDs) have emerged as promising catalysts for the hydrogen evolution reaction (HER) that play a crucial role in renewable energy technologies. Breaking the inherent structural paradigm limitations of 2D TMDs is the key to exploring their fascinating physical and chemical properties, which is expected to develop a revolutionary HER catalyst. Herein, we unambiguously present metallic W2S3 instead of energetically favorable WS2 via a unique stoichiometric growth strategy. Benefiting from the excellent conductivity and hydrophilicity of the tetra‐coordinated structure, as well as an appropriate Gibbs free energy value and an enough low energy barrier for water dissociation, the W2S3 as catalyst achieves Pt‐like HER activity and high long‐term stability in both acidic and alkaline electrolytes. For application in proton exchange membrane (PEM) and anion exchange membrane (AEM) electrolysers, W2S3 as the cathode catalyst yields excellent bifunctionality index (ɳ =1.73 V, ɳ =1.77 V) and long‐term stability (471 h@PEM with a decay rate of 85.7 μV h−1, 360 h@AEM with a decay rate of 27.1 μV h−1). Our work provides significant insight into the tetra‐coordinated W2S3 and facilitates the development of advanced electrocatalysts for sustainable hydrogen production.

Mo2C-Based Ceramic Electrode with High Stability and Catalytic Activity for Hydrogen Evolution Reaction at High Current Density.

Developing robust electrodes with high catalytic performance is a key step for expanding practical HER (hydrogen evolution reaction) applications. This paper reports on novel porous Mo2C-based ceramics with oriented finger-like holes directly used as self-supported HER electrodes. Due to the suitable MoO3 sintering additive, high-strength (55 ± 6MPa) ceramic substrates and a highly active catalytic layer are produced in one step. The in situ reaction between MoO3 and Mo2C enabled the introduction of O in the Mo2C crystal lattice and the formation of Mo2C(O)/MoO2 heterostructures. The optimal Mo2C-based electrode displayed an overpotential of 333 and 212mV at 70°C under a high current intensity of 1500 mAcm-2 in 0.5m H2SO4 and 1.0m KOH, respectively, which are markedly better than the performance of Pt wire electrode; furthermore, its price is three orders of magnitude lower than Pt. The chronopotentiometric curves recorded in the 50 - 1500 mAcm-2 range, confirmed its excellent long-term stability in acidic and alkaline media for more than 260h. Density functional theory (DFT) calculations showed that the Mo2C(O)/MoO2 heterostructures has an optimum electronic structure with appropriate *H adsorption-free energy in an acidic medium and minimum water dissociation energy barrier in an alkaline medium.

Hierarchically Porous Carbonized Wood Decorated with MoNi4‐Embedded MoO2 Nanosheets: An Efficient Electrocatalyst for Water Splitting

AbstractDevelopment of low‐cost electrocatalysts for water splitting is crucial to economical hydrogen production. Here, a highly efficient electrocatalyst composed of MoNi4‐embedded amorphous MoO2 nanosheets grown on less‐tortuosity hierarchically porous carbonized wood (MoNi4/MoO2@CW) is reported. The generation of abundant MoNi4/MoO2 heterointerfaces and defects‐rich MoO2 significantly promote the adsorption and activation of reactant molecules on the MoNi4/MoO2@CW. The obtained MoNi4/MoO2@CW catalyst exhibits ultralow overpotentials of 22 and 205 mV for hydrogen evolution reaction and oxygen evolution reaction at a current density of 10 mA cm−2, respectively. The catalyst can be used for dual‐function electrodes and assembling two‐electrode electrolyzer illustrates 10 mA cm−2 at 1.47 V and superior durability over 24 h for overall water electrolysis. Moreover, it also possesses a high mass activity of 142 Ag−1 MoNi4 at 200 mV, surpassing the Pt/C catalyst (132 Ag−1). The outstanding performance of the MoNi4/MoO2@CW is attributed to the decrease in energy barrier for water dissociation, optimal adsorption/desorption of H/O‐intermediates, and fast mass transport through the porous structure, as confirmed by experimental results and density functional theory‐based calculations. The MoNi4/MoO2@CW electrocatalyst has excellent potential for practical water splitting.

Asymmetric orbital hybridization in Zn-doped antiperovskite Cu1−xZnxNMn3 enables highly efficient electrocatalytic hydrogen production

Rational design of efficient and robust earth-abundant alkaline hydrogen evolution reaction (HER) catalysts is a key factor for developing energy conversion technologies. Currently, antiperovskite nitride CuNMn3 has garnered significant interest due to its remarkable properties such as negative/zero thermal expansion and magnetocaloric effects. However, when utilized as hydrogen evolution catalysts, it encounters large challenge resulting from excessively strong/weak interactions with adsorbed H on Mn/Cu active sites, which leads to low HER activity. In this study, we introduce an asymmetric orbital hybridization strategy in Zn-doped Cu1−xZnxNMn3 by leveraging the localization of Zn electronic states to reconfigure the electronic structures of Cu and Mn, thereby reducing the energy barrier for water dissociation and optimizing Cu and Mn active sites for hydrogen adsorption and H2 production. Electrochemical evaluations reveal that Cu0.85Zn0.15NMn3 with x = 0.15 demonstrates exceptional electrocatalytic activity in alkaline electrolytes. A low overpotential of 52 mV at 10 mA cm−2 and outstanding stability over a 150-h test period are achieved, surpassing commercial Pt/C. This research offers a novel strategy for enhancing HER performance by modulating asymmetric hybridization of electron orbitals between multiple metal atoms within a material structure.

Interface and morphology engineering of Ru-FeCoP hollow nanocages as alkaline electrocatalyst for overall water splitting

Interface and Morphology engineering strategies of electrocatalysts are of great importance to promote water splitting performance, although still facing many challenges. In this work, we present a facile method for preparing Ru-anchored hollow FeCoP nanocages electrocatalyst with ultrathin sheets. The hollow structure composed of ultrathin nanosheets and rich heterogeneous interfaces benefit the as-synthesized catalyst to exhibit small overpotentials of 310 mV and 94 mV at the current density of 10 mA·cm−2 for oxygen evolution reaction and hydrogen evolution reaction, respectively. When Ru-FeCoP nanocages were employed as the bifunctional catalyst for overall water splitting, the potential of 1.65 V was obtained to reach the current density of 10 mA·cm−2. The experimental results confirmed that the formation of hierarchical hollow structure facilitated the exposure of active sites and enhanced the electrocatalytic activity. Meanwhile, XPS and DFT data also reveal that the presence of heterogeneous interfaces changed the electronic structure, optimized the absorption of the intermediates, significantly reduced the energy barrier of water dissociation and promoted the release of H2. This work offers an effective route for rational design of low-loading noble metal-anchored metal phosphide with the hierarchical hollow structure and rich interfaces towards overall water splitting.

Atomic-level coupled RuO2/BaRuO3 heterostructure for efficient alkaline hydrogen evolution reaction

The slow water dissociation is the rate-determining step that slows down the reaction rate in alkaline hydrogen evolution reaction (HER). Optimizing the surface electronic structure of the catalyst to lower the energy barrier of water dissociation and regulating the binding strength of adsorption intermediates are crucial strategy for boosting the catalytic performance of HER. In this study, RuO2/BaRuO3 (RBRO) heterostructures with abundant oxygen vacancies and lattice distortion were in-situ constructed under a low temperature via the thermal decomposition of gel-precursor. The RBRO heterostructures obtained at 550 °C exhibited the highest HER activity in 1 M KOH, showing an ultra-low overpotential of 16 mV at 10 mA cm−2 and a Tafel slope of 33.37 mV dec−1. Additionally, the material demonstrated remarkable durability, with only 25 mV of degradation in overpotential after 200 h of stability testing at 10 mA cm−2. Density functional theory calculations revealed that the redistribution of charges at the heterojunction interface can optimize the binding energies of H* and OH* and effectively lower the energy barrier of water dissociation. This research offers novel perspectives on surpassing the water dissociation threshold of alkaline HER catalysts by means of a systematic design of heterogeneous interfaces.

Synergistic reaction kinetics of Pt single atoms/MoS2 and nanoparticles for energy-saving hydrogen production assisted by green electrosynthesis of azotetrazolate compound

Overall water splitting (OWS) involves two important half-reactions, namely hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). However, due to the high theoretical overpotential of OER, OWS needs to be realized with high energy consumption. Using anodic oxidation reaction with lower theoretical potential to replace oxygen evolution reaction (OER) can effectively reduce the energy consumption of overall water splitting (OWS) for hydrogen production. Here, we introduce a new oxidation reaction of green electrosynthesis of energetic materials (EMs) and coupled with OWS. The catalyst was prepared by electrodepositing Pt nanoparticles (Pt NPs) and Pt single atoms (Pt SAs) on MoS2 nanosheets, which drives highly-efficient hydrogen production of 35.6 mV to drive 10 mA cm−2. DFT calculations reveal the synergistic mechanism of Pt NPs and Pt SA/MoS2 substrate for promoting hydrogen production, is that the energy barrier of water dissociation was reduced on the Pt NC sites and the produced H* migrated to the adjacent S sites for Heyrovsky step, while the Pt SA sites served as electron regulator for more thermoneutral H* adsorption on S sites, realizing the synergistic reaction kinetics in MoS2/Pt for promoting alkaline HER. Importantly, by integrating the OWS and electrosynthesis of 5,5′-azotetrazole (ZT) EMs, the cell voltage can be significantly reduced to 1.29 V at 10 mA cm−2, realizing low-energy-consumption for hydrogen production. Meanwhile, the green electrosynthesis of ZT is achieved to avoid the hazardous process of traditional preparation methods. This study presents a new strategy for green electrosynthesis of EMs and low-energy-consumption hydrogen production.

Titanium-doped copper oxide/ruthenium heterostructure constructed on Cu3Ti nanosheet for efficient hydrogen evolution reaction in alkaline media

Platinum group metals (Pt, Ru, Ir, etc.) are the most active catalysts for acidic hydrogen evolution reaction (HER), yet they cannot deliver satisfactory performance in alkaline media owing to the high energy barrier of water dissociation. Here, we report the outstanding alkaline HER performance of Cu3Ti-supported Ti-doped CuO/Ru (Cu3Ti@CTO/Ru) heterostructure catalysts, which were fabricated simply by an impregnation-heat treatment method. Density functional theory calculation results indicate that the energy barriers of both water dissociation and hydrogen desorption at CTO/Ru heterointerface are significantly reduced relative to Ru catalyst alone. As a result, the Cu3Ti@CTO/Ru catalyst at the optimum Ru loading amount achieves a low overpotential of 34 mV at the current density of 10 mA cm−2 and an ultra-low Tafel slope of 29 mV dec-1 in 1 M KOH, outperforming the benchmark 20% Pt/C catalyst. This study provides new insight into the development of advanced alkaline HER catalysts.

Greatly Boosting Seawater Hydrogen Evolution by Surface Amorphization and Morphology Engineering on MoO2/Ni3(PO4)2

AbstractHydrogen production through seawater electrolysis faces several challenges, one of which involves the development of electrocatalysts with high catalytic performance. Here, surface amorphization and morphology engineering are combined to design a novel electrocatalyst for highly‐efficient hydrogen evolution reaction (HER). The surface‐amorphized MoO2/Ni3(PO4)2 microcolumns supported on nickel foam (SA‐MoO2/Ni3(PO4)2/NF) display remarkable performance with low overpotentials of 34 and 46 mV at a current density of 10 mA cm−2 in 1 m KOH and alkaline seawater, respectively. In addition, the alkaline electrolysis cell (AEC) integrated with SA‐MoO2/Ni3(PO4)2/NF as the cathode and Ni foam as the anode achieves a current density of 100 mA cm−2 at 1.87 V in 6 m KOH seawater at 60 °C, superior to that of industrial NiMo electrode as cathode (2.05 V). DFT calculations demonstrate that the surface amorphous layer (MoOx) improves the hydrogen adsorption energy of sample and reduces the energy barrier of water dissociation. It is found that substantial improvement in catalytic performance stems from the synergistic effect between surface amorphization and unique microcolumn morphology. These findings may provide insights into combining surface amorphization and morphology engineering strategies to enhance catalytic performance and pave the way for the development of highly efficient seawater HER electrocatalysts.

Turing structuring with multiple nanotwins to engineer efficient and stable catalysts for hydrogen evolution reaction

Low-dimensional nanocrystals with controllable defects or strain modifications are newly emerging active electrocatalysts for hydrogen-energy conversion and utilization; however, a crucial challenge remains in insufficient stability due to spontaneous structural degradation and strain relaxation. Here we report a Turing structuring strategy to activate and stabilize superthin metal nanosheets by incorporating high-density nanotwins. Turing configuration, realized by constrained orientation attachment of nanograins, yields intrinsically stable nanotwin network and straining effects, which synergistically reduce the energy barrier of water dissociation and optimize the hydrogen adsorption free energy for hydrogen evolution reaction. Turing PtNiNb nanocatalyst achieves 23.5 and 3.1 times increase in mass activity and stability index, respectively, compared against commercial 20% Pt/C. The Turing PtNiNb-based anion-exchange-membrane water electrolyser with a low Pt mass loading of 0.05 mg cm−2 demonstrates at least 500 h stability at 1000 mA cm−2, disclosing the stable catalysis. Besides, this new paradigm can be extended to Ir/Pd/Ag-based nanocatalysts, illustrating the universality of Turing-type catalysts.

Competitive Adsorption Mechanism of Defect‐Induced d‐Orbital Single Electrons in SrRuO3 for Alkaline Hydrogen Evolution Reaction

AbstractIn the alkaline hydrogen evolution reaction (HER), the dissociation energy barrier of water, and the easy adsorption of OH on the catalyst are key factors that limit the catalytic activity. This work proposes a novel competing adsorption mechanism driven by dz2 electrons in the context of the alkaline HER. The high concentration of oxygen vacancies in Co doped SrRuO3 (V‐SRCO) results in the electron filling in the Ru 4dz2 orbital. Under alkaline conditions, the V‐SRCO exhibits a low overpotential of only 57.8 mV with a Tafel slope of 35 mV dec−1. Moreover, it exhibits sustained high activity for 60 h. The high HER activity of V‐SRCO can be attributed to the presence of a single electron in the dz2 orbital, which reduces the energy barrier for water dissociation. More importantly, the active electrons in the dz2 orbital can inject into the antibonding orbitals of OH, creating an unfavorable environment for OH adsorption on the catalyst. This work provides favorable conditions for efficient HER.

Waste biomass-derived N, P co-doping carbon aerogel-coated CoxFe1−xP with modulated electron density for efficient electrooxidation of contaminants

Developing low-cost, green, high-performing electrode materials to address environmental pollutants and the energy crisis is significant but challenging. Herein, the bimetallic iron cobalt phosphide coated in waste biomass-derived N, P co-doping carbon (CoxFe1−xP@NPC) is constructed. Furthermore, the active site density and the water decomposition energy barrier of surface-coated NPC are modulated by optimizing the electronic structure of CoxFe1−xP via doping engineering. The Fe-modulated CoxFe1−xP@NPC exhibits a hierarchical porous self-supporting structure and excellent physical & chemical properties with excellent electrooxidation performance, achieving over 95% removal of TCH within 60 min. The density functional theory (DFT) calculations further confirms that N carries more positive charge and P carries more negative charge in the NPC of CoxFe1−xP@NPC with Fe modulation, which can promote the adsorption and dissociation of water molecules. Of note, Co0.75Fe025P@NPC displays a low water dissociation energy barrier to produce ·OH and a high energy barrier to produce O2 than its counterparts. This study offers new insight into controllable modulation of biomass carbon-based composite electrode catalytic activity for high-efficiency degradation of contaminants.

Hierarchical SiC-Graphene Composite Aerogel-Supported Ni-Mo-S Nanosheets for Efficient pH-Universal Electrocatalytic Hydrogen Evolution.

MoS2 exhibits good prospects in electrocatalytic hydrogen evolution. Whereas, the electrocatalytic property of MoS2 is restrained by its insufficient active sites, low electrical conductivity, and slow water dissociation processes. Herein, an aerogel composed of silicon carbide (SiC) and graphene (SiCnw-RGO) was constructed by growing SiC nanowires (SiCnw) in the graphene aerogel (RGO) via the CVD method, and then Ni-Mo-S nanosheets were hydrothermally synthesized on the SiCnw-RGO composite aerogel to develop an efficient pH-universal electrocatalyst. Ni-Mo-S nanosheets supported on SiCnw-RGO (Ni-Mo-S@SiCnw-RGO) exhibit an interesting hierarchical three-dimensional interconnected structure of composite aerogel. The optimal Ni-Mo-S@SiCnw-RGO electrocatalyst exhibits excellent catalytic performance with low Tafel slopes of 60 mV/dec under acidic conditions and 90 mV/dec under alkaline conditions. Density functional theory calculations demonstrate a composite catalyst exhibits advantageous hydrogen adsorption free energy and water dissociation energy barrier. This study provides a reference to design an efficient hierarchical aerogel electrocatalyst.